Epoxy alkyl esters of polybasic aromatic carboxylic acids and process of making same



State EPOXY ALKYL ESTERS F POLYBASIC ARO- MATIC CARBOXYLIC ACIDS AND PROCESS OF MAKING SAME Bernhard Raecke, Rudolf Kiihler, and Helmnt Pietsch, Dusseldorf, Germany, assignors to Henkel & Cie, G. in. h. H., Dusseldorf-Holthausen, Germany, a corporation of Germany No Drawing. Application September 14, 1953 Serial No. 380,133

application Germany September 20, 1952 6 Claims. (Cl. 260-484) Claims priority,

This invention relates to epoxy alkyl esters and more particularly to epoxy products derived therefrom.

Another object of this invention is to provide the crystalline terephthalic acid diglycide ester.

A further object of this invention is to provide products which are of great value in the plastics and artificial fiber industry.

Still another ether, furthermore a,'fi-bis-(p-carboxy phenyl) ethane, and others.

Especially suitable halogenides for said reaction are the chlorides and bromides. The chlorides, however, are the preferred halogenides since they are readily available and comparatively inexpensive.

Glycide may be replaced in said reaction by equihydroxyl groups, for instance, 4-hydroxy butylene-1,2- anhydropentoses, anhydrohexoses (hydroxy methyl), oXa-cyclobutane, oleyl alcohol-oxide-9,l0, and others.

The reaction is preferably carried out in the presence of agents capable of splitting ott hydrogen halide, i. e. of hydrogen halide In general, the reaction proceeds in thecold or at room temperature. If necessary, it may be completed by gently 7 heating the reaction mixture.

Patented Dec. 23, 1958 The products formed in this reaction are the diglycide esters or homologuous esters of the corresponding polybasic aromatic carboxylic acids. These esters may be further condensed to higher molecular, non-distillable, resinous condensation products, containing several glycide ester groups in their molecule. Whether the reaction yields the one or the other of these types of reaction the preferred one, depends, among others, upon the reaction duration, reaction temperature, manner of Working up the reaction products, and under certain conditions, upon the presence of moisture. v,

As stated above, the new epoxy alkyl esters'arevaluable intermediates, especially in the plastics and artificial fiber industry. v

The reaction product is worked up in a very simple manner. The hydrogen halogenide of the base added to the reaction mixture can be removed from said mixture by washing with water. Or in case an indifferent diluting agent, such as toluene, benzene, benzine, carbon tetraa hydrochloric The following examples serve to illustrate this invention without, however, limiting the same thereto.

EXAMPLE 1 obtained thereby weighs 290 g. Toluene is removed from the filtrate by distillation at a bath temperature up to C. and at a vacuum of about 10 mm. mercury. The residue (230 g.) has the following characteristic properties and analytical value:

Epoxide-oxygen content percent 8.1 Nitrogen content do 0.87 Chlorine content "Traces Saponification number I' 394 Molecular weight 250 On distilling said product, finally at a bath temperature of and in a vacuum of 0.7 mm. mercury until no Epoxide-oxygen content percent 7.0

Nitrogen content do 1.4

Chlorine content Traces Saponification number 420 Molecular weight 480 EXAMPLE 2 A solution of 20.6 g. of pure terephthalic acid chloride in 100 cc. of benzene is added drop 29 g. of precipitated triethylamine hydrochlo ride are filtered otf, preferably after standing overnight Analytical data calculated found for CuHu Percent Percent Epoxide-oxygen content .11. 7 11. Carbon 60. 60. 4 Hydrogen -6. 2 5. 0

In place of phthalic acid dichloride and terephthalic acid dichloride as used in the preceding examples there may be employed the'chlorides and bromides of other polybasic aromatic carboxylic acids in equimolecular amounts. Likewise, equimolecular amounts of other epoxy compounds containing hydroxyl groups, than glycide as used in said examples, such as 4-hydroxy butylene =1,2-oxide, anhydropentoses, anhydrohexoses, (hydroxy methyl) oxa-cyclobutane,'oleyl alcohol-oxide-9,10, and others, may be reacted with such halogenides. In place of triethylamine-one may-use other tertiary organic nitrogen bases as hydrogen "halidebinding agents. It is not necessary to carry out the reaction in the presence of =adiluting agent although such agents permit better control of the reaction temperature and prevent too high an increase thereof.

Other changes and variations inthe starting materials employed, the acid binding agent used, the reaction temperature and duration, the diluting agent added to the reactionmixture, the methods of working up said reaction mixture and of isolating the desired reaction products therefrom, the condensation of the resulting diglycide esters or their homologues to resinous condensation products containing several glycide ester groups in their molecule, and the like may be made by those skilled in the art in accordance with the principles set forth herein and in the claims annexed hereto.

We claim:

' '1. A process of producing glycide esters of aromatic hydrocarbon dicarboxylic acids and resinous epoxy polymers thereof comprising the steps of reacting at temperatures up to roomternperatures anaromatic hydrocarbon dicarboxylic acid halide with .glycide in the presence of a sufiicient amount of atertiary .amino compound to react stoichiometrically with the hydrogen halide produced.

2. The process of .claiml wherein thearomatic hydrocarbon dicarboxylic acid halide is a phthalic acid dihalidc.

3. A process of producing resinous epoxy polymers of diglycide esters of aromatic hydrocarbon dicarboxylic acids comprising the steps of reacting at temperatures up to room temperatures an aromatic hydrocarbon dicarboxylic acid dihalide with glycide in the presence of a sufitcient amount of a tertiary amino compound to react stoichiometrically with the hydrogen halide produced, removing the amino hydrogen halide salt, and stripping the residue of unreacted constituents and monomers by distillation in a high vacuum.

4. A process of producing diglycide esters of aromatic hydrocarbon dicarboxylic acids comprising the steps of reacting at temperatures up to room temperature an aromatic hydrocarbon dicarboxylic acid dihalide with glycide in the presence of a sufiicient amount of a tertiary amino compound to react stoichiometrically with the hydrogen halide produced and removing the amino hydrogen halide salt.

5. A process of producing a diglycide ester of terephthalic acid comprising the steps of reacting at temperatures up to room temperature terephthalic acid dichloride with glycide in the presence of a sufficient amount of triethylamine to react stoichiometrically with the hydrogen chloride produced, said reactants being dissolved in a solvent selected from the group consisting of benzene, toluene and carbon tetrachloride, removing the insoluble triethylamine hydrogen chloride salt and excess solvent, and crystallizing pure diglycidyl terephthalate from the concentrated solution.

6. A proces of producing resinous epoxy polymersot diglycidyl phthalate comprising the steps of reacting at temperatures up to room temperature phthalic acid dichloride with glycide in the presence of a sutficient amount of triethylamine to react stoichiometrically with the hydrogen chloride produced, said reactants being dissolved in a solvent selected'from the group consisting of benzene, toluene and carbon tetrachloride, removing the insoluble triethylamine hydrogen chloride, distilling oil the solvent and stripping the residue of unreacted constituents and monomers by distillation in a high vacuum.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS OF PRODUCING GLYCIDE ESTERS OF AROMATIC HYDROCARBON DICARBOXYLIC ACIDS AND RESINOUS EPOXY POLYMERS THEREOF COMPRISING THE STEPS OF REACTING AT TEMPERATURES UP TO ROOM TEMPERATURES AN AROMATIC HYDROCARBON DICARBOXYLIC ACID HALIDE WITH GLYCIDE IN THE PRESENCE OF A SUFFICIENT AMOUNT OF A TERTIARY AMINO COMPOUND TO REACT STOICHIOMETRICALLY WITH THE HYDROGEN HALIDE PRODUCED. 